Method of producing valuable materials



Nov. 21, 1944. J. E. HARVEY, JR., ET AL l 2,363,239

METHOD'OF PRODUCING VALUABLE MATERIALS Filed Nov. 18, 1942 )Own-envi ferner/0m 004/055? may be put.

Patented'Nov. 2l, 1944 -12,3t3,z39 I 'l UNITED 'STATESWPATENT ori-uci;

. ME'rnoD or raonuome VALUABLE Muslims Jacqueiin E. HarveLJr., Washington, D. C., and Robert H. White, Jr., and Joseph A. Vaughan,-

Atianta, Ga., assixnors of one-half to said Har i vey, Jr., and one-halt to Southern Wood Preserving Company, East Point, Ga., a corporation of Georzia Application November 18, 1942, Serial No. 466,054

, (ci. 19e-sz) 12 Claims.

The instant invention relates the production of toxic oils employable 'las funsicides, insecticides, and for any ,other service to which toxic oils More especially the instant inventionv relates to the production of toxic oils from mixtures of petroleum fractions characterized by ring structure content. Among such starting materials may be mentioned mixtures of petroleum fractions characterized by ring structure content recovered from petroleum fractions by well known extraction methods including extractive distillation and azeotropic distillation. Also may be mentioned mixtures of petroleum fractions characterized by ring structure content as flowing from thermal and/or catalytic treatment of certain petroleum fractions which includes petroleum fractions having ring structures induced in the course oi' thermal and/or catalytic treatment,

` as for example having ring structures inducedjinthe course of one or more thermal and/or catalyticl treatments of unusual length, as for example, for periods of from 1-10 hours or more.

An object of the instant inventionA is the pro- .f

duction of toxic oils from the aforenamed petroleum fractions or others whereby to provide oils of the preservative type, as for example preservative wood' impregnants conforming-to specifications extant oracceptable to the trade conn suming such oil materials.

Another object of the instant invention is the provision of preservative wood impregnants hav ing boiling ranges and residues in accordance with published specifications and/or in accordance with consumer preference.

Another object of the instant invention is the reforming, modifying, converting and/or transforming of the mixtures o1' hydrocarbons whereby to induce toxicity. Still another object of the instant invention of a gas or gaseous mixtures.

Another object of the instant invention is the unveilingl of latent toxicity in mixtures of l'petrolem fractions having inherent but inhibited tox- 1c y.

l the induction of usable toxicityin the presenceV Another object of the instant invention is the maintenance of a preponderant proportion of the cyclic structures in the material undergoing toxicity induction in at least a methylated condition, it having been found that objectionable reaction products are formed if this object is not adhered to.

Another object ofthe invention is the control of saturates in specific fractions of the material undergoingtreatment.

sau another object of the instant-invention is' the control of the percentage of cyclic structures, as for instance aromatics, in speciiic fractions of the beneciated material which is characterized by induced toxic properties.

Yet another object of the instant invention is the provision in the overall beneflciated materialv of that percentage4 of newly induced fractions coordination of process variables .which will provide 'in various fractional parts of the beneiiciated material cyclic structures with speciiic,` gravities falling within the limits hereinafter stated.

.Another` object of the instant invention is the induction'of toxicity in the presence of a reforming catalyst adapted to favorably influence the induction of toxicity. By the expression a reforming catalyst is meant a catalytic material adapted to exert catalytic influence whilst the starting material is being reformed, transformed, modified and/or` converted. In the specification and in the annexed claims, reformation, transformation, conversion and/or modification of the starting material whereby to induce toxicity is specifically meant to include cracking, addition, and substitution reactions that are possible within the limits of the ,process variables disclosed elsewhereherein. y

Another object of the instant inventlonis the induction of additional toxicity into fractional parts of the once beneflciated starting material under specific controls of process variables.

In the past wood preservative oils ofthe high temperature coal tar derived type have been employed in quantities greatly exceeding the total From the' of al1 other wood preservative oils. standpoint of availability of said coal tar as the parent product of wood preservative oils, itis annually produced in this country-under normal conditions to the extent of live hundred million to six hundred million gallons. This quantity of coal tar is capable oi yielding an amount of highly edective wood preservative oils which would make this country self-sufficient in its wood preservative requirements. fact that when a wood preservative distillate (creosote) is recovered from coal tar there remains in the still a residue (pitch) which, at best, is a low priced product and which, at worst, is a seriously distress product to the end that at times it is placed in inventory rather than sold, national creosote requirements are notproduced in this country. The current method of processing coal tar leaves much to be desired. The net result of this situation obtaining is that the coal tar distiller usually connes himself to that distille tion recovery of creosote which would correspond to the attending amount of pitch that he can market at a profit. Accordingly, over a period of years several hundred million gallons of i creosote oil have been imported into this country. That such a situation should obtain is apparently a paradox in that we annually produce a quantity of high temperature coal tar which if yprocessed to yield creosote would make us self sufthe lucrative wood preservative market. At the present time many types of aromatic oils are produced by the petroleum industry, and the high boiling oils of aromatic content produced by this industry have for several years been tested for their wood preservative emciency.

By the term "petroleum aromatic as used lslovvever,- due to thev Gravity 10.8 Flash, P. M. C. C F 295 Flash, C. 0. C; F. 290 Fixed carbon percent 4.9 y Pour point --F -10 B. S. Bz W percent by volume-- 0.1 S. U. vis. 100 FL-; 151 S. U. vis. @l 210 F 1 v41 e S. F. vis. 77 F 34.5v Carbon residue 6.8 Percent aromatics and unsaturates 82.4 Sol. in CS2- 99.8 Loss 50 grams, 5 hours, 325 F 8.9 'Residue of 100 pene -percent-- 37.5

A. S. T. M. distillation:

I, B. P F 518 10% Rec. F 565 Rec. l@ F 589 Rec. F 614 Rec. @l F y637 Rec. F 660 Rec. F. 1 675 'nery of the Shell Oil ,Company and 'which has the following inspection:

Martin Closed Cup; C. 0. C. means Cleveland Open Cup.

herein and inthe appended claims is meant to include mixtures of petroleum fractions characterized by cyclic content and to include specifically various forms and types of naphthenes found in various mixtures of petroleum fractions, as for example monocyclic and polycyclic naphthenes. l l

The so-called petroleum aromatics which includes the monocyclic and polycyclic naphthenes 'and unsaturated hydrocarbon fractions have in the past been produced in very large quantities. However, very little work has been doneon these materials. Such a fact is borne out on page 667,

Reactions of pure hydrocarbons, Gustav Eglo, Reinhold Publishing'. Corporation, 330 West 42nd Street, New Yori: city, which states:

"Despite the fact that naphthenes or cycloparamnes are available in enormous quantities, as shown by an estimate of 100,000,000 barrels present in the 1,490,000,000 barrels ofv crude oil which was the worlds production in 1934, coinparatively little vwork of a pyrolytic nature has been performed on individual naphthene hydrocarbons or the cycloolelns."

Several oils of cyclic content produced by the petroleum industry have been inspected for their toxicity to wood destroying fungi, among which mayV be mentioned a high boiling Aoil of cyclic content produced (i940) at the Wood River Re- Upon evaluating the foregoing oil for its tcxicity to wood destroying fungi (Madison 517), it was found that this oil did not inhibit the growth of, the fungi 'named at a concentration content produced by the petroleum industry are reformed, transformed, modified and/or convertedto oils of/a more toxic nature having characteristics acceptable to consumers of wood preservative impregnant and/or conforming to wood preservative specifications extant. 'I'he accompanying drawing is a flow sheet of theprocess. The following examples will serve to illustrate several modes of practicing the present invention.

Example 1.A mixture of petroleum fractions characterized by cyclic content having but slight growth inhibition to wood destroying fungi, as

for example the Shell product shown inthe foregoing tabular data, is charged to a vessel adaptedA drawn from the processing chamber, cooled and inspected. Upon inspection the oil is found to have toxic properties unveiled as the result of the treatment above named, and such induction of toxicity is accompanied and evidenced by the production oi' the named percentage of newly induced fractions boiling below 210 C.

In the induction of toxicity in accordance with the instant process, it has been determined that unless at least about 10% newly formed fractions boiling below 210 C. are induced, latent toxicity is not unveiled to the desired extent. It

has also been determined that if more than about the instant method, the process variables are'so coordinated as to maintain a preponderant pro-` portion of the cyclic structures of the materials under ,treatment in at least a methylated condition. it having been found that an attempt to totally dealkylate the cyclic structures of the starting material results in the `formation of toxicity diluents, inordinate gasification and/or the formation of substantially non-toxic substances. The expression in at least a methylated condition refers to the number of carbon atoms in the ring appendages. Each fraction of the benelciated material of induced toxicity, as for example and especially the materials boiling between 315 C. and 355 C., has a preponderant proportion of materials of cyclic structure present in at least a methylated condition.

Conditions that are prejudicial 'to the main.

tenance of a preponderant proportion of the cyclic structures of the starting material in at least a methylated condition are excessive temperatures and/or excessive time of treatment,

Temperatures that are employable in the instant process which will provide the aforenamed end result are D-550 C., and preferably between 40G-500 C., say 430 C. to 480 C. Using the preferred temperature whilst operating at superatmospheric pressure, as for example at pressures ranging between G-3000 pounds, it will be "found that selected between the limits of when the treatment is carried on for a period of one to two hours the end product will have induced toxicity as flowing from, among other things, the maintenance of a preponderant proportion of the materials of ring structure content of the starting material in at least a methylated condition, and accompanied with and indicated by a percentage of newly formed fractions boiling below210 C. falling between the limits of about lil-50%, and the induction of toxicity is enhanced by the specific inclusion of a reforming catalyst.

The pressure employed in the instant process may be autogenous due to the pressure of evolved vapors, or the pressure may be provided by any means well known to the art, as for example by pumping and/or valving arrangements.

The material of induced toxic properties as iiowi'ng from the process carried out under the controls above disclosed may be used in toto as a woodpreservative or in the event it is desired to provide a preservative wood impregnant cornplying with specications extant or of consumer preference, a wood preservative may be segregated from the overall benefciated oil vas a stabilized residual, distillate or extract and in the event the extract has non-permissible low boiling ends, the extract maybe stabilized to the.

necessary or desired extent.

As examples of wood preservative impregnants of the oil derived type that are meeting with consumer preference and which may be produced or paralleled by the process of the present invention, the following tabularv data show several published specifications:

Woon PREsERvATxvE IMPREGNANTS Specifications l. American Wood Preservers Association a. Up to 210 C., not more than 5% b. Up to 235 C., not more than 25% 2. American Wood Preservers Association a. Up to 210 C., not more than 1% b. Up to 235 C., not more than 10% c. Up to 355 C., not less than 65% 3. American Wood Preservers"` Association a. Up to 235 C., not'more than l1/2% b. Up to 300 C., not more than ll/2% c. Up to 355 C., not less than 45% 4. American Wood vlreservers Association a. Up to 210 C., not more than 8% b. Up to 235 C., not more than 35% 5. American Wood Preservers Association a. Up to 210 C., not more than 10% b. Up to 235 C., not more than 40% 6. American Wood Preservers Association a. Up to 210 C., not more than 5% b. Up to 235 C., not more than 15% '7. Prussian Ry.

a. Up to 150 C., not more than 3% b. Up to 200 C., not lmore than 10% c. Up to 235 C., not more than 25% 3. National Paint 'Varnish 8i Lacquer Association #220 a. 5% at 162 C. b. 97% at 270 C. 9. Southern pine shingle stain oil a. 5% at 137 C. b. at 257 C. Neville shingle stain oil a. I. B. P., C. b. 5% at 205 C.

c. 95% at 292 C. 11. Carbolineum .270 C., I. B. P.

If desired, the processing of the oil may be carried on in the presence of an extraneous gas whose partial pressure may vary over wide ranges, as for example the partial pressure of the extraneous gas may be 5-50% or more. Among the extraneous gases employable are hydrogen. carbon monoxide, carbon monoxide and water vapors, methane and its homologues, various renery gases and inert gases such as nitrogen and carbon dioxide. Certain special benefits ow from carrying on the toxicity induction in the presence ofv an extraneous gas. among which may be mentioned the thermal protection oi'- the material under treatment, as for example when employing hydrogen or a hydrogen containing' gas the material under treatment is not so susceptible to polymerizing reactions. This provision, in one mode of Aoperation is to be specifically read into the foregoing example, and in the event it is elected to carry on the process in the presence of a reactive gas, as for instance hydrogen, the suppression of polymerizin'gr reactions is more pronounced and is especially beneficial. Y

In the event it is elected to employ carbon` monoxide and water, the total pressure may vary over` wide limits, as for example from 200 to 5,000` pounds, or higher. In likemanner the carbon monoxide partial pressure may vary ovei``fwide i limits, as for instance, from 5to 50 percent, or higher. The water may represent from 5 to 50% or higher based on the oil under toxicity inducing conditions, and in some instances may represent more than twice the amount of the charged oil. In, one mode of operation, this definite teaching `concerning the employment of carbon monoxide and water is to be specifically read into all examples. The carbon monoxide and water may be introduced simultaneously with the feed stock, or at other times, separately or jointly.

Example 2.-A liquid sulfur dioxide extract is chargedy to a high pressure autoclave and hydrogen pumped in to an upper pressure of 1,000 pounds. Three percent of a reforming catalyst is employed. The material is heated to atemperature of 450 C. and held at that heat tone for a period of one hour and minutes. maximum pressure of 2050 pounds is attained when a heat tone of 425 C. is reached.

At the end of the named processing period, the oil is discharged from its treating enclosure, cooled and inspected. It is found that 19.2%

' newly formed materials boiling below 210 C. have been formed, and the beneciated oil requires `a smaller concentration for a given growth inhibition of wood destroying fungi than the starting material. It is also determined that a preponderant proportion of the materials of cyclic structure content in the treated oil has been maintained in at least a methylated condition.

The overall beneficiated material may be used as a preservative impregnant of induced toxic properties, or a preservative impregnant of the desired boiling range maybe segregated therefrom.

Eample 3.-Another mode of practicing the instant process whereby to induce toxic properties resides in the control of saturates in the beneficiated material boiling above 270 C., as for example the materia boiling between 270 C. and 355 C.

It has been determined that the materials boiling above 270 C. in the beneciated oil have a relatively low toxicity as comparedto materials boiling below that temperature. It is known that unsaturates are amongst the most toxic of oil substances. However, it is also determined that if an attempt is made to provide in the beneficiated oil of induced toxic properties, the entirety of the materials boiling above 270 C., as for example the materials boiling between 270 C. and 355 C., as unsaturates, adverse reactions occur that are prejudicialv to the induction of toxicity as for example there occurs (1) inordinate gasification, (2) inordinate production of materials of relatively little toxicity and/or (3) polymerized high boiling materials.

When providing acceptable toxicity in the overall reformed, transformed, modified and/.or converted oil, it has been determined that by holding the percentage of saturates in the materials boiling above 270 C., as for example in the materials boiling between 270 C. and 355 C., to less than 30% but more than 5%, and preferably not more than 10%,` no operating ills such as 355 C., inherent but inhibited toxicity and having 41% and 34%l saturates, respectively, inthe 27o-315 C. and S15-355 C. fractions, is subjected to a liquid phase thermal treatment in the presence of a pelleted silicious clay and hydrogen at a temperature of 445 C. for a period of one and one-half hours whilst under a pressure of 1800 pounds.v At the end of the named period of treatment the beneficiated oil is discharged from its treating enclosure, cooled and inspected. The beneciated oil has only 28.5% residue above 355 C. and it is determined that there are only 23.3% and 12% saturates, respectively,.in the 27o-315 C. and 315-355 C. fractions. lThe oil has toxic properties that are more pronounced than the parent feed stock. vDuring the course of treatment 18.1% of newly formed materials boiling below 210 C.,were formed. A further vinspection of the beneiiciated material discloses that a preponderant proportion of the cyclic structures of the starting material was maintained in at least a methylated condition.

A variation of the process described in Example 3 may be provided by carrying on the process in the absenceof hydrogen, and certain toxicity benefits will iiow therefrom. The provision of carrying on the process withouta protective gas of extraneous source is, in one mode/ of operation, to be specifically read into Example 3.

Eample 4. -An oil of cyclic content produced by the petroleum industry having inherent but inhibited toxicity, an initial boiling point of about 270 C., about 50% residue above 355 C. `and 52% and 54% aromati'l, respectively, in the 270-315" C. and B15-35.5 fractions, is subjected to a liquid phase thermal treatment in the presence of a reforming catalyst and hydrogen ata temperature of 455 C. for a. period of one hour and 30 minutes. At the end of the named period the treated oil is withdrawn from the processing enclosure, cooled and inspected. It is found that about 22% newly formed fractions boiling below 210 C. have been formed. The residual matters aboveI 355 C. have been reduced by in excess of 45%. The fractions of the beneciated material boiling between 270-315 C. and S15-355 C. have 71% and 80.5% aromatics, respectively. The overall beneficiated oil is characterized by a toxicity more pronounced than the startingrnaterial.

It is well understood in the art'that the aromatics, as for example aromatics having side chains not longer than the propyl group are amongst the most toxic of all substances. As stated in the foregoing, the feed stock in the instant example has slightly more than 50% aromatics in the 270-355 C. fraction. However, the

aromatics present, due to their peculiar type,

exhibit inhibited toxicity. It would then, therefore, appear reasonable to attempt to provide in the finally beneciated oil total aromaticity in the materials boiling between 270 C. and 355 C. in order to induce toxicity of a high order, and more Vespecially it would appear reasonable to attempt to provide total aromaticity of a type 4 reactions occur which are prejudicial to a ,satisfactory induction of toxicity, as for example there occurs (1) inordinate gasification, (2) inordinate production of materials of relatively low toxicity and/or (3) high boiling polymerized materials. "1

It is found that by holding the percentage of aromatica in the materials boiling above 270 C.

in the benenciated oil, as for example the beneiiciated materials boiling between 270 C. and 355 C., to more than 70% but less than 95%, and preferably not less than 90%toxicity/is induced in a commercial manner with the added benefits that the operating ills above mentioned are minimized or eliminated.

The oil of the instant example, as stated in the foregoing, has toxic properties more pronounced than the parent feed stock, and may be used in toto as a preservative wood impregnant. This phase of theinstant invention, in any and all examples, resides in the novel manner of inducing toxic properties without reference to thepro-Z vision of specification oils. However, as also previously mentioned, specification oils may be segregated from the overall beneilciation.

In lieu of practicing the process as specically provided in Example 4, the process, in one `mode #of operation, may be specifically carried` on without the presence of a protective gas of extraneous source and an increase of toxicity will flow from this mode of practice. However, the increase of toxicity when providedv by thermal treatment inV the absence of a protective gas is not as satisfactory as when carried on in the presence of the protective gas. I

Example 5.-Another mode of practicing the whereby to provide a beneiiciated material re limits of 0.015 and 0.15%, and preferably between 0.020% and 0.10%. Such a stated change in specic gravityhas the eiiect of inducing\and indicating the induction of toxic properties into materials previously having inhibited toxic values. The lowering of the specific gravity within the defines stated is critical within limits. Unless an overall specic gravityof the material under treatment is 4lowered by 0.015%, a certain unveiling of inhibited toxicity is sacrificed, and if the overall specific gravity is lowered by more than 0.15%, inordinate gasiilcation, production v of fugitive materials of relatively low toxic value `and/or polymerization will occur. To avoid or minimize these ills, and/or others, the reduction of specic gravity -is preferably held between 0.020% and 0.10%.

Certain toxicity benefits will flow from carry--v ing on the process of Example 5 without the lnclusion of the protective gas of extraneous source.

j In one 4mode of operation, this provision of carrying on the process without a protective gas of extraneous source is to be specifically read into that part of Example 5 which providesfor the lcwering of the overall specific gravity of the feed s ock.

In connection with the change in specliiic gravv ity of the overall starting material which results instant process resides in controlling the specific in the induction of toxicity, a modication of the ably between 0.020 andJ 0.10. l

To illustrate this modincation of the instant process `an oil oi cyclic content produced by the petroleum industry having relatively little toxicity, as for example a flashed residuum having .a specific gravity Aof 0.924 and a substantial per- 40 centage of materials boiling above 355 C. is submaining finally liquid having, as compared to the parent feed stock, an overall change in specific gravity between 0.015 and 0.15, and preferably Vbetween 0.020 and 0.10,` the material of the jected to a liquid phase thermal treatment in the presence of a reforming catalyst and a saturated hydrocarbon gas at a temperature selected between the limits 'of 450-525" C. whilst underl a pressure of 1200 pounds -forsuch a period of time as to provide an overall beneiiciated material remaining iinallyliquid having a specinc gravityof 1.015. yWhen the stated specific gravity has been attained the beneflciatedmaterial will have sub-- stantial residual matter above 355 C. A period gravity which is conducive to the induction of toxic properties may be either up or down, as

more fully disclosed and explained in the follow-f toxicity, boiling preponderantly above 315 C. and

with substantial residual matter above 355 C., is subjected to a liquid phase thermal treatment in the'presence of a reforming catalyst and a hydrogen containing gas at a temperature of 465 C.

whilst under a pressure of 1500 pounds for. a

period of two hours. At the end of the named` treatment period the oil is cooled and inspected and found to have a specific gravity of 0.940 or a reduction in specific ygravity of 0.020%. The

overall beneciated material has induced toxic properties and more vthan 10% but less than'50% newly formed fractions boiling below 210 C.A

.According to this specic mode of operational ess variables arefso coordinated Vas to cause a reduction in speciiicgravityfalling `between the of froin one to ve hours dependent upon the temperature selected will illustratively serve for the stated' increase of specific gravity.

The oil of the stated increased specific gravity 06 is inspected land found to have toxic properties control and test in the instant example, the procmore pronounced than its parent feed stock. The beneiiciation in toto may be usedy as a preservative wood impregnant or, as taught in the foregoing, an impregnant of induced toxic prop- .gg erties having. ,a specification boiling range may be segregated therefrom. v In lieu of increasing the specific gravity whil employing-a gas of extraneous source, the process l. may, in one mode of operation, be practiced without the added gas. When increasing the specific gravity with the exclusion of anextraneous gas, the increase of the specic gravity is held within the limits noted in the foregoing.

Example 6.--An oil containing materials of cyclic structure content produced by the petroleum industry, as for example a liquid sulfur dioxide or furfural extract, having inherent but lnhibited toxicity, boiling 15% at 315 C., and about 45% residual matter above 355 C., is charged to l a high pressure autoclave and subjected to a liqbetween the limits of 0.015 and 0.15,` and preferuid phase thermal treatment in the presence of a reforming catalyst and water gas at a temperature selected between 43o-185 C. whilst'under a pressure of 1700 pounds for such a time as parts of the benenciated oil falling within the limits noted in the following tabular data:

accesso C. is heat treated in the liquid phase Iin the presence of a reforming catalyst and hydrogen `at a temperature selected between the limits -of 435- 475 C. whilst under a pressure of 1800 pounds for such a length of time as to jointly provide more than 10% but less than 50% newly formed fractions boiling below 210 C., and a specific gravity of materials of cyclic structure content in fractional' parts of the beneflciated material l@ falling between the limits noted in the following Fractions Low 11mm mgniimc tabular data:

0.20i 1.0048 Fractions Low limit High limit 0&50 l. 0315 0.914 1. com 0.913 1.1115 0,913 rosso 0.936' 1.0756 0.973 i 1.0933 and preferably between, the limitsnoted below: 1 027 1-1285 When processing the named oil and operating at the stated pressure and a temperature of 455 C., a period of one and one-half hours will provide a specific gravity in fractional parts of the beneciated material falling between the preferred stated limits, and will also provide the stated percentage of newly formed materials boiling below 210 C.

servative oil, which insome instances boils almostl entirely above 270 C.

The specic gravities of fractional parts of the beneciated material noted in the foregoing are critical within limits. Unless the lower limit is approximated toxicity unveiling wil1he sacrificed. If the high limit is substantially exceeded adverse 'reactions will occur, as for example there will be inordinate gasification and/or production of highly polymerized and objectionable materials.

Instead of practicing the process disclosed in the immediate example vby employing a protective gas of extraneous source, this mode of operation may be carried on without a gas of extraneous source with the resultant approximation of the noted specific gravities. 'Induced toxicity will also flow from the practice of this process variation.

Example 7.-In lieu of inducing toxicity Whilst providing operationiail control of the overall specic gravity of fractional parts of the beneflciated material as heretofore disclosed, the control may be gauged by the provision of predetermined speciiic gravities of materials of cyclic structure content in fractional parts of the beneclated material. v

As an example, an oil of cyclic structure conand preferably between 4the limits noted below:

Fractions Low limit High limit 21o-235 C 0. 941 1.0430 2135-270" C 0. 963 1.0606 270-3l5 C 1.001 1.0783 B15-355 C. 1.055 1. 1135 When processing the named oil Aat a pressure and temperature of 1800 pounds and 460 C., re-

spectivelyya period of about one hour and 15" minutes will illustratively provide a specific gravity of materials of cyclic structure content in fractional parts of the beneciation failing between the stated preferred limits.

When the beneficiatlon isV inspected it is found to have toxic properties more pronounced than the parent material. 1

The provision ofspeciilc gravities of materials of cyclic structure content in fractional parts of the beneilciation noted in the foregoing is critical within limits. Unless the ylower limit is approximated toxicity induction is sacrificed. If the high limit is exceeded adverse reactions will obtain, as for example there will occur inordinate gasication and/or production of highly polymerized materials.

In the mode of operation which induces toxicity whilst providing the stated increase of specific grav/ities in the materials of cyclic structure content. this process variation may. be specifically l practiced without the protective gas of extraneous source.

Erample 8.-Referring specifically to the overall beneciated material of induced toxic propl erties produced by the process variations of the foregoing examples, itis found that the materials boiling below and above 270 C. have relatively high and low toxicities, respectively. It is discovered that additional toxicity may be induced into the beneflciated material by subjecting same to another toxicity inducingcycle at' s.

' higher temperature than obtained in the4 first cycle of toxicity induction provided the retreat-v ment yet maintains a preponderant percentage of materials of ringstructure contentin at least a methylated condition. Referring specifically to tent produced by the petroleum industry having with in excess of 30% residual matter above 355 the overall once beneciated material of Example -1, this beneiiciation is subjected to another toxlcityinducng cycle in the liquid phase in the presence of a reforming catalyst and hydrogen at a temperature .of 450 C. whilst under a pressure of 850 pounds. 'Ihe retreatment is continued for a period of 45 minutes. The stated period is illustrative only. The retreatment period is desirably that which provides inthe finally toxic `propertio'es `in excess of the overall once beneiiciatedoill lIt is also determined that the finallybeneciated material yet maintains a preponderant proportion of the cyclic materials in at least a methylated condition.

When retreating` the overall once beneficiated material, the,1 process may specically be carried on without the inclusion of the protective gas of extraneous source, vand toxicity beneiits will flow from thisi'iractitze.` l i Example 9`,In lieu of retreating the entirety of `the once `beneficiated material at a more elevated temperature, only a portion thereof may he retreated in the liquid phase in the presence of a reforming catalyst, `with. or without the pres ence of a protective gas of extraneous source, and certain definite toxicity increases and beneiits will flow therefrom, as for example by retreating in liquidphaseonly the materials of relatively low toxicity boiling above 270 C. Or, the retreatment of materials boiling above 270 C., or a portion thereof, maybe effected at the same temperature-as the initial treatment. When. the materials ofirelatively lowA toxicity are retreated for added toxicity induction at either of the temperatures aforenamed, the retreated material when commingled `with that portion of the starting `material once beneficiated will provide a comminglementhaving toxic properties in excess of those of the"-once treated oil.

Instead of` commingling the entirety of the onceitreated materials and the twice treated materials, only a portion thereof may be commingled provided the* comminglement` furnishes an oil conforming in boiling range to consumer acceptance or provides alcomminglement'from which may besegregated an oil of consumer acceptance.

The retreatment temperatures are selected betweenthe limits `of 30G-550 C. and preferably betweenl425'-500"\C. A

Example 10.-Practice the process of Example l with a molybdenum oxide catalyst.

Example `11o- Practice the process of Example with a chromium oxide catalyst. K Example 12.-Practice the process of Example with a vanadium oxide catalyst.-

Example 13.-Practice the process of Example with a `tin oxide catalyst.

`Example 14.-Practice the process of Example with amolybdenum sulfide catalyst.

Example 15.-Practice the process of Example with a chromium sulfide catalyst. Example 16.-Practice the process of Example withY a vanadium `sulde catalyst.

2Example 17.-Practice the process of Example 8 with a tin sulfide catalyst.

Example 18.-Practice the process of Example 9 with the coprecipitated oxides of copper and chromium as catalytic materials.

Example 19.-Practice the process of Example l with tin chloride as catalytic material.

Example 20.-`Practice the process of Example 2 `with aluminum chloride as catalytic material.

Example 21.-Practice the process of Example 3vwith iodine as catalytic material.

Example 22.--Practice the process of Example 4 with iodoform as catalytic material.`

Example 23.--Practice the process of Example 5 with hydroiodic acid as catalytic material.

Example 24.-Practice the process of Example 6 with chlorine as catalytic material. y

Example 25.-Practice the process of Example 'l with bromine as catalytic material.

Example 26.--Practice the process of Example 8 with a hydrogen halid as catalytic material.

Example 27 .-Practice the process of Example 9 with ammonium chloride as catalytic material.

Example 28.--Practice the process of Example.

l with pelleted bentonite clay as catalytic material.

Example 29e-Practice the process of Example 2 with activated attapulgus clay as catalytic material.

Example 30.-Practice the process of Example 3 with a silica hydrogel as catalytic material.

Example 31.-Practice the process of Example 4 with a silica hydrogel impregnated withv an aluminum salt as catalytic material.`

Example 32.-Practice the process of Example 5 with bentonite and an adsorptive clay as catalytic materials.

Example 33 Practice the process of Example 6 with a silicious material impregnated with a metallic oxide as catalytic material.

Example 34.-Practice the process of Example 'l with a silicious material impregnated with a metal sulde as catalytic material.

Example 35.-Practicethe process of Example 8 with ,coprecipitated alumina and chromia hydrogels as catalytic materials.

ployable either in the material remaining liquid' under process controls, or in the evolved vapors, or both. Other than the catalysts mentioned in the foregoing, also employable are the various metals and their carbonates, cellulosic materials and carbon, activated or otherwise. Especially effective as catalytic materials are the halogens, halids and derivatives thereof, including specilically substitution and addition products thereof, as for example and speciiically substitution and addition products of said derivatives, say a hydrogen halid.

The temperatures of the instant prbcess, in any and all steps, are selected between the limits of 300-550 C., and preferably between 42E-500 C. The pressures employed in the instant process are in excess of atmospheric and are specifically those pressures required for operation in the i liquid phase. rIfhe term liquid phase may not ,be technically correct, but as used herein and in the annexed claims is meant to 'distinguish from the so-called vapor phasel operation which employs vaporized materials only.

If desired, instead of' subjecting the entirety of the feed stock to a single toxicity inducing operation, the parent material may be segregated into a plurality of cuts and these plurality of cuts subjected to separate toxicity inducing operations wherein the temperatures in each instance are dissimilar, as for example, but not as a restriction, subjecting the highest boiling cut to the lowest temperature, etc.

In the examples shown in the foregoing, one or more phases, etc., of one example may vbe added to or substituted for other phase or phases in an-V .extraneous gas.

other example where the substitution or addition is obviously workable.

The evaluation of the/materials of cyclic structure content ,and/or aromatics referred to in the foregoingl is secured by recourse to the method disclosed under the caption Neutral oils of coal hydrogenation-Action of sulfuric acid, Industrial and Engineering Chemistry, volume 32, page 1614 et seq., December, 1940. i

Many modes of practicing the instant process are possible. As for example the oils of inherent but inhibited toxicity mentioned in the foregoing may be subjected to a destructive distillation under pressure in the presence -of a reforming catalyst, with or without the presence of a protectivegas of extraneous source,\and toxicity induced therein. The following disclosures will enable those skilled in the art to practice such a process, at the same time adding details which will immediately suggest themselves as routine and non-inventive improvements.

If desired, `a mixture of petroleum fractions characterized by cyclic content, as for example the Shell product shown in the foregoing tabular data, having inherent but inhibited toxicity is charged to a still adapted to operate at superatmospheric pressure which communicates with a condenser. The catalyst is selected from the materials aforementioned. Intermediate the still and the condenser is an appropriate needle valve adapted to regulate the pressure within the still due to the pressure of evolved vapors, or jointly due to the evolved vapors and the presence of an 'Ihe still is so arranged that evolved vapors are at least partially reluxed. The reflux ratio may vary over Wide limits and different eiects ow from varying percentages l of reflux. Air is expelled from the still during lthe preliminary heating period and the lneedle valve then closed so as to develop the desired pressure Within the still due at least partially to the pressure of evolved vapors. It is preferred to carry on the destructive distillation in the presence of a protective gas of extraneous source. as for example hydrogen or a hydrogen containing gas. 'I'he needle valve is then partially opened,` and the valve aperture, heat control and reflux so coordinated as to provide a relatively constant ow of evolved vapors through the needle valve aperture.

Operatingat a pressure of, as an example a hundred pounds or higher, say many hundreds of pounds, it is found that the oil under distillation is reformed, transformed, modified and/or convertedl and toxicity induced therein. It is also found that the temperature necessary for matassa as the protective gas of extraneous source. in this or other examples, the hydrogen may speciiically be secured from carbon monoxide and water in a well known manner.

While Examples 10 to 36 disclose the use of deflnite catalysts with definite ones of the Ex-.

amples 1 to 9 inclusive, it is to be understood that these catalysts are interchangeable with the definite controls of the early examples, and any of thenamedcatalysts or their equivalents are usable in any of the Examples 1 to. 9. The examples given, and the catalysts linked therewith are for purposes of illustration only.

A very attractive form of carrying out a modified mode of the instant process is by inducing toxicity into the starting material in the presence of nitrogen or carbon dioxide. Thus, one mode of operation specifically provides ,for nitrogen and/or carbon dioxide as the protective gas or gases of extraneous source.

Minor changes within the scope of the annexed claims may be made without departing from the spirit of the invention.

We claim: n

rl. The process of inducing toxicity into a petroleum derived material, which comprises: subject-ing a mixture of petroleum fractions boiling preponderantly above 270 C., characterizedby a substantial percentage of relatively non-toxic materials boiling above 315 C., ring structure content and inherent but inhibited toxicity to liquid phase-cracking conditions in the presence.

of a reforming catalyst at a temperature selected between the limits of 300 C. and 550 C. anda pressure in excess of atmospheric; unveiling toxicity in the material under treatment by continuing the named cracking operation for a period not in excess of about two hours, the period being so selected with reference to the chosen temperature and pressure as to jointly provide a percentage of newly induced materials boiling below 210 C. falling between the limits of about 10-50% and fractional parts of the overall beneficlated oil containing materials of cyclic structure content the distillation of any given percentage of the r feed stock is considerably higher than for the distillation of a comparable percentage under substantially atmospheric pressure.

As the distillation proceeds the temperature isl gradually raised so as to maintain a relatively constant flow of distillate. Thedistillation is carried to the desired extent, as for example for the distillation reforming of 80% or more of the feed stock, or the distillation may be ycarried to the greatest extent possible. The time neces sary for the distillation of al given charging stock will be determined by the speed of firing, percentage of reflux, etc., and the process may be illustrated by recovering 3-10% of the still charge per hour as materials of induced toxic properties.

If desired, the distillate may be redistilled under a similar destructive` distillation to provide additional toxic properties.

In .the event it is elected to employ hydrogen having a specific gravity falling substantially between thelimits noted in the appended tabular data: e f

Fractions Low limit High limit whereby to provide a material of induced toxic y properties; and segregating from the beneflciated material an oil of the wood preservative type boiltroleum derived material, which comprises: subj'cting a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by a substantial percentage of relatively non-toxic materials boiling above 315 C., ring structure content and inherent but inhibited toxicity vto liquid phase cracking conditions in the presence` of a reforming catalyst selected from the group consisting of oxidesand sulfldes of heavy metals at a temperature selected between the limits of 300 C. and 550 C. and a pressure in excess of atmospheric; unveilingtoxicity in the material under treatment by continuing the named cracking operation for a period not in excess of about two hours, the period being so selected with reference to the chosen temperature and pressure as to` jointly provide a'percentage of newly induced materials boiling below 210 C. falling between the limits of about l-50% and fractional parts oi' the o verall beneiiciated oil containing materials of cyclic structure content having a specific gravity falling substantially between the limits noted in the appended tabular data:

' Fractions Low limit High umn 0.1113` 1.0580 0.935` 1.0155 0.973 1.0933 1.1m 1.12ct

whereby to provide a material of induced toxic properties; and' segregating from the beneflciated material an oil of the wood preservative type treatment by continuing the named cracking opl boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxicity to wood destroying fungi and substantial residual matter `boiling above 315 C., the fractions of which have speciicgravities i'alling between the limits above named. i 1 f 4. The processl of claim 3 with inclusion of carrying on the cracking operation in the presence of a protective gas of extraneous source.v

5. The process of inducingtoxicity into a pe-y troleum derived material, which comprises: subjecting amlxture'of petroleum fractions boiling preponderantly above 270- C., characterized by a substantial percentage of relatively non-toxic i materials boiling Vabove 315 C.,.ring structure content and inherent lbut inhibited toxicity to liquid phase cracking `conditions in the presence of a reforming catalyst selected from the group consistingof halogens. halids and derivatives thereof including substitution and addition products thereof and substitution and addition products of the latter at a vtemperature selected between the limits of 300 C. and 550 C. and a pressure in excess of atmospheric; unveiling toxicity in the material under treatment by` continuing the named cracking operation for a period not ln excess of about two hours, the period being so selected with reference to the chosen temperatureand pressure as to jointly provide a percentage of newly induced materials boiling below 210 C. falling between the limits of about 10-50% and fractional parts of the overall beneficiated oil` containing materials of cyclic structure content having a specic gravity falling substantially between the 'limits noted in the appended tabular data: l

Fractions Low limit High limit 0. 913 1. 0580 o. 935 1. 075e l 0. 973 1. 0933 l. 027 1. 1285 whereby to provide a material of induced toxic properties; and segregating from the benelciated material ali oil of the wood preservative type 15 boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxicity to wood destroying fungi and substantial residual matter boiling above 315 C., the fractions of which have speciiic gravities falling between the limits above named.

6. The `process of claim 5 with inclusion of carrying on the cracking operation in the presence of a protective gas of extraneous source.

7. The process of inducing toxicity into a petroleum derived material, which comprises:

subjecting a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by a substantial percentage of relatively nontoxic materials boiling above 315 C., ring structure content and inherent but inhibited toxicity to liquid phase cracking conditions in the presence of a reforming catalyst of silicious content at a temperature selected between the limits 'of 300 C. and 550 C. and a pressure in excess of atmospheric; unveiling vtoxicity in the material under eration for a period not in excess of about two hours, the period being so selected with reference to the chosen temperature and pressure as to jointly provide a percentage of newly inducedmaterials boiling below 210 C. falling between the limits of about l0-50% and fractional parts o f the overall beneilciated oil containing materials of cyclic structure content having a. specific gravity falling substantially between the limits noted in the appended tabular data:

Low limit High limit o. 91a 1. osso o. 93s 1. 015s o. 97a 1. 0933 1.021 1; 1285 .whereby to provide a material of induced toxic properties; and segregating from Vthe beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxicity to wood destroying fungi and substantial residual matter boiling above 315 C., the fractions of which have specific gravities falling between the limits above named. l

8. The process of claim 7 with inclusion of carrying on the cracking operation in the presence of a protective gas of extraneous source.

9. 'I'he process of inducing toxicity into a petroleum derived material, which comprises: subjecting a mixture of petroleum fractions rboiling lpreponderantly above 270 C., characterized by a substantial percentage of relatively non-toxic materials boiling above 315 C., ring structure content and' inherent but inhibited toxicity to liquid phase cracking conditions in the presence of a I reforming catalyst at a temperature selected be-` tween the limits of 300 C. and 550 C. and a pressure in excess of atmospheric; unveiling toxicity in the material under treatment by continuing the named cracking operation for a period not in excess of about two hours, the period being so selected with referenceV to the chosen tempera- -ture and pressure as lto jointly provide a percentage of newly induced materials boiling below 210 C. falling between the limits of about lll-50%, and fractional parts of the overall -beneciated oil containing materials oi cyclic structure content having a specific gravity Afalling substantiallybetween the limits tabular data:

noted in the appended Fractions Low limity High limit zas-270 C 0.935 1. 075s 27o-315 C 0. 97s 1. ccas whereby to provide a material of induced toxic properties: and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly -between 210 C. and 355A C., said oil characterized by induce-d toxicity `to wood destroying fungi and substantial residual matter' boiling above 315 C., the fractions of named cracking operation for a period not in excess of about two hours, the period being so selected with reference to theichosen temperature and pressure as to jointly provide a percentage of newly induced materials boiling below 210 C. falling between the limits of about 1050%, and fractional parts of the overall beneficiated oil containing materials of cyclic structure content having a specific gravity fallingv substantially which have specific gravities falling between the limits above named.

10. The process of inducing toxicity into a petroleum derived material, 'which' comprises:

subjecting a mixture of petroleum fractions -boiling preponderantly above 270 C., characterized by a substantial percentage of .relatively nontoxic materials boiling above 315 C., ring structure content and inherent but inhibited toxicity to liquid phase cracking conditions in the presence of a reforming catalyst at a temperature selected between the limits `of ,300C. and 550 C. and a pressure in excess of atmospheric; unveiling toxicity in the material under treatment by continuing the named cracking operation for ya period not'in excess of about two hours. the period being so selected with reference tothe chosen temperature and pressure 'as to jointly provide a percentage of newly induced materials boiling below 210 C. falling between the limits of about 10-50%, and fractional parts of the overall -beneiciated oil containing materials of cyclic structure content having a specific gravity falling substantially between the limits noted in the appended tabular data:

Fractions Low limit High limit 270-3l5 C l 0.973 1.0933 a15-355 C i 1.027 1.1285

whereby to provide a material of induced toxic properties; and segregating from the beneficiated material an oil ofthe wood preservative type boiling preponderantly between2l0" C. and 355 C., said oil characterizedby induced toxicity to wood destroying fungi and substantial residual matter boiling above 315 C., the fractions of which have specific gravities falling between the limits above named.

11. The process of inducing toxicity into a petroleum derived material, which comprises:

whereby to provide a material of induced toxic l properties; and segregating from the benetlciatedy material an oil of the wood preservative type -boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxicity to woodldestroying fungi and substantial residual f matter boiling above 3l5 C., the fractions of which havev specific gravities falling Abetween the 1 toxic materials boiling above 315 C., ring structure content and inherent but inhibited toxicity to liquid phase cracking conditions in the presence of a reforming catalyst selected from the group consisting of oxides and sulides of metals at a temperature selected between the limits of 300 C. and 550 C. and a pressure in excess of atmospheric; unveiling toxicity vvin the material under treatment by continuing the named cracking operation for a period not in excess of about two hours, the period -belngso selected with reference to the chosen temperature and pres- .sure as to jointly provide a percentage of newly induced materials boiling below 210-C. falling between the limits of about 10-50%, and fractional parts of the overall -beneciated oil containing materials of cyclic structure content having a Aspecific gravity falling substantially between the limits noted in the appended tabular data:

Fractions Low limit High limit 270-315 C .0. 973 l. 0933 31o-355 C 1.027

whereby to provide a material of induced toxic properties; and segregating from the beneflciated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized byinduced toxicity to wood destroying fungi and substantial residual matter boiling above 315 C., the fractions of which have specific gravities falling between the limits above named.

JACQUELIN HARVEY, JR.

ROBERT H. WHITE, Jn.

JOSEPH A. VAUGHAN. 

